Thienyl vat dye compounds and vat dye intermediates and processes for their preparatiion



Patented Oct. 20, 1953 THIENYL VAT DYE COMPOUNDS AND VAT DYE INTERMEDIATE FOR THEIR- PREPAR S AND PROCESSES ATION James M. Straley and Raymond C. Harris, Kingsport, Tenn., assignors t 'pany, Rochester, N. Y

Jersey Eastman Kodak Coma corporation of New No Drawing. Application March 29, 1951, Serial No. 218,264

8 Claims. (Cl. 260-3293) 3 4 5 6 WT'EI 2 7 1105 2 -o-on=on,

I II

IO-methylene- Z-thienylvinylketone anthrone Bz 1-(2-thenoyl) benzanthrone The various nuclei are numbered as indicated above. Y

The new vat dye compounds of the invention are prepared by ring closing the Bz l-thenoylbenzanthrone vat dye intermediate compounds. The course of the reaction is believed to be as illustrated hereinafter:

' Base upon as being pyrene-1,6-dione, the new vat dye compounds of the invention can be termed 2,3- thienyl-7,8-benzo-pyrene-1,6-dione compounds. Under this nomenclature, the compound numbered IV is 2,3-(2,3-thienyl)-7,8-benzo-pyrene- 1,6-dione. That is, the thienyl nucleus is joined through its 2- and 3-positions to the 2- and 3- positions of the pyrenedione nucleus and a benzene nucleus is joined to the 7- and 8-positions of the pyrenedione nucleus. As indicated hereinafter, where a Bz 1-(3-thenoyl) benzanthrone compound is employed rather than a. Bz 1-(2- thenoyl) benzanthrone compound 2,3-(3A-thienyl)-7,8-benzo-pyrene-1,6-dione vat dye compounds are obtained, that is, the thienyl nucleus is attached through its 3- and 4-positions to the 2- and 3-positions of the pyrenedione nucleus.

It is an object of the invention to provide new vat dye compounds. Another object of the invention is to provide new valuable vat dye intermediates which are probably Bz l-thenoylbenzanthrone compounds. A further object is to provide satisfactory processes for the preparation of the new compounds of the invention.

In preparing the new Bz 1-thenoy1benzan-' throne compounds of the invention, a 10-methyleneanthrone which is unsubstituted in at least one of the 4- and 5-positions is condensed with a thiophene vinyl ketone. The condensation reaction is ordinarily carried out in the presence of a solvent such as acetic acid, nitrobenzene or o-nitrotoluene, for example. Further, the use of a mild oxidant has been found to be beneficial and is preferred. Oxidants that can be employed include, for example, air, oxygen and nitrated aromatic hydrocarbons'such as nitrobenzene, 0- nitrotoluene, m-nitrotoluene or p-nitrotoluene, for example. The reaction can be carried out at any suitable temperature. However, the'use of temperatures of C. or above is preferred. Temperatures of about 160C. to about C., for example, are suitable. 'Some oxidants can serve both as the oxidant and the solvent. To

were obtained as a yellow solid melting at about 170 C. It dissolves in concentrated H2804 with a red coloration.

Following the procedure set forth in Examples 1 to 4, inclusive, other vat dye intermediates of the invention can be prepared. Thus, 32 1-(2- thenoyl) 7 methylbenzanthrone, B2 1 (2- thenoyl) -l-fluorobenzanthrone, Bz l-(Z-thenoyl)-6 methylbenzanthrone, Bz 1 -[3- (2,5 dichlorothenoyl) l-fi-chlorobenzanthrone, Bz 1- [3- (2,5-dichlorothenoyl) l-7-ch1orobenzanthrone, B2 1 (2-thenoyl)-5-methylbenzanthrone and Bz 1 (3-thenoyl)-7-chlorobenzanthrone, are also readily prepared.

Preparation of vat dye compounds EXAMPLE 5 An intimate mix of 17 parts of B2 1- ('2-thenoyl) benzanthrone and 10 parts of M1102 (90% pure) were added to a melt of 160 parts of A1C13 and 80 parts of NaCl at 150 C.160 C. Heating was discontinued during this operation because of the exothermic character of the reaction. The reaction mixture was then held at 185 C.-190 C. for two to three hours, poured onto ice, boiled and filtered. The filter cake thus obtained was washed with water until neutral and then dissolved in a solution of 20 parts of sodium hydroxide and 20 parts of sodium hydrosulfite in 2000 parts of water at 60 C., filtered and the filtrate blown with air. The filter cake obtained on filtration was placed in dilute aqueous NaOH and treated with sodium hypochlorite at 70 C.-80 C. until no further change took place. The reaction mixture was then filtered and the product obtained on the filter was washed well with water and dried; Sixteen parts of 2,3-(2,3-thienyl) 7,8-benzo-pyrene-1,6-dione having the formula:

were obtained as an orange solid. It dyes cotton fast golden yellow shades from a scarlet vat. It"

of A 1Cla and 200 parts of NaCl at C470 (1., the heat source being removed during the addition because of the exothermic character of the reaction. The remainder of the process was carried out in accordance with the procedure described in Example 5. Fourteen parts of 2,3-[3,4- (2,5 dichlorothienyDl 7,8 benzo pyrene- 1,6-dione were obtained as an orange powder. It dyes cotton fast (especially to light) shades of orange from an orange-red vat and has the formula:

EXAMPLE 7 The process of Example 5 was followed omitting the MnOz. In place of M1102, a slow stream of oxygen was passed into the reaction mixture for ten hours while maintaining the reaction mixture at C.-- C. Twelve to 14 parts of a product identical with the product of Example 5 were obtained. I

EXAMPLE 8 An intimate mix of 17 parts of B2 1-[3-(2 ,5- dichlorothenoyD] benzanthrone and 20 parts of MnOz (67%) were added to a melt of 600 parts of A1013 and 200 parts of NaCl at 150 C.-170 C., the heat source being removed during the addition because of the exothermic character of the reaction. The reaction mixture was allowed to stand for 2.5 hours and then 6 parts of bromine were slowly added and the reaction mixture al lowed to stand for 3 hours longer. Upon working up the reaction mixture in accordance with the procedure described in Example 5, 17 parts of an orange-brown powder dyeing cotton fast shades,

'. that are slightly redder than those obtained with the product of Example 6, from a red vat were obtained. a

,7 EXA PLE 9 To a dyestuff melt prepared exactly as described in Example 5, there were added slowly after 2 hours 10 parts of bromine. After addition of the bromine the reaction mixture was allowed to stand for 3 hours, after which it was worked up in accordance with the procedure described in Example 5. Nineteen parts of a product dyeing cotton fast orange shades from a scarlet :vat were obtained.

EXAMPLE i0 below 80 C. When no more chlorine was takenup by the reaction mixture, the reaction mixture wasdrowned in water and the reaction mixture thus obtained was filtered. The product obtained on the filter was purified by treatment with'sodium hypochlorite. Twenty parts of a product which dyes cotton fast orange shades from a red vat were obtained.

EXAMPLE 1-1 An intimate mix of 19 parts of Ba .1 1Y i l b emb e e i 0 Parts 9 90%) were addertto a melt at. 160? patent A101: and 80 parts ot i Na-tli at;1-50 -b16080.andv the reaction was conducted and.- the reaction mixture worked up inaccordance with the procedure described in, Example Sixteenparts ct 2,3---( 2-;3- thienyl) 7-,8-- (2 ch1orobenzo) --pyrene 1,6- dione. were) obtained; as; orange.- powdem It has theionmula;

and dyes cotton golden orange shades from a red vat.

By the use of 19 parts oi, Bz 1-(2'-thenoyl)- 'T-chlorobenzanthrone and 13 parts of Bz 1-(2- thenoyl -5?methylhenzanthrone; respect-ively; in place of -Bo l tz -thenoyli'-6 chlorobenzanthrone im the above example; 2,3-('2;3 thienyll' 'iiii (3 chlbrobenzoY-pyrene-li6 dione and 2 ,3 -('2;3"-thi'- enyUflZSHf-methylbenzo)-pyrene-l;6 -dione, respeotively; areoiitainmfi iexmrnnwle An. intimate mix of 22 parts; of: the: product at Example 4; (in e.-. 1.- 3-(2;5 -dich1omthen' oylLl-fi-methylbenzanthrone) and parts: of (90%); were; addedato: amerit of: 160: artsofi AlClqi EDdifiQiPBltS-Df: NaGliat =150 (L-160 G3 and the reaction was-conductedrand the-reaction mixture worked upt iniaccordancel-with the' proiceduredescribedgin Example 5: Seventeen par-ta 01 23.-

kfiedichlomthienyn 1 '-'7,8*(-2:.--methyJ:- benzolf-pyrene-l fi-dione; wereobtained: as. an orangemowdeni lthasxtheiormuflaz.

andrdxes. cottomorazigetshades fromia;scarit vat;

By; the} uses of? 23.-1r pa1'.ts of IBz' -1"-'[3'- (2;5 di=- chlorothenoyl) lfiechibrobenzanthrone' and 2574* parts of B2 1-[3- (2, 5-diehlorothenoy1)1-8-bromobenzanthrone. respectively.. in place of. B2 1"- [3 (25 di'chlorothenoyll l -6. methylbenzanthrone in the:- above example; 213'; [3,4 (215:6?- chlorothienyi) ]-7i8- (2-ch1orobenzo)' pyrene- 1",6=dione and? 2,3 "-[3,4 (2;5 dfch1orothienyl)'1 7i8=4 lromohenzo9= -p'yrene= lifi dionef. respeetiveii'; are obtained? Following the= procedure described hereinbe fore; other vat dyecompounds' of the=-invention beeprepared; To illustrate; 2,8 (2,23'- thien= yt). H28; (-Hbromobenw) pyrene l;6-dione,= 2,3 (2;3'thieny1i :-'7',8:'-'(-1I'-fluorobenzo) --p'yren'e 1113* dione, l 2,33 wv (2;3i'-thienyl) -728-=(1 chloroben*zo) pyrene-1,6-dione, 2,3 [3,4-(25=dihlorothien*-' yi) ]-7,8-(l-fluorobenzo pyrene-1,6-dione and 2,3- (3,4 .thienyll-7.8-.(2Pch1orobenzo) pyrene- 1;6 -id1one are also readilig prepared;

8 invention perrormedi according. to the usual stnonge-alicalia vatv procedure-n Dyeing. can; be caazriediout as follows: 0-.05' gram of dyestuff are well ground with a few dropsof Monopol oil (sulfonatedt caster-oil): and rinsed into a;- dye= bath. The dye-bathis brought to' a total vol ume of 100 cc., using. soft water, and 0.5-1 gram of NaOH and 0.75-1' gram of sodium hydrosulthe are adiiedi The temperature of the dyebath is raisedto C. and 5" grams of a well wet cut" cotton goods areentered and dyedat 51) (Cl-55 C. for 1 hour; The dyed' cloth is removed, rinsed and hung in aifu'ntil oxidation is complete Thedyeings are finished" by a 20 m'inuteboili'na 05% aqueous sodium ca rhoriate solution; rinsing" with" water" and drying. While the manner in which my" new vat dye compounds are applied to cotton; for example, constitutes" no" part or my invention; it will be understood" that the dyeing procedure" given aboveis merely illustrative and not lirhitative" oi the manner in which theymay he applied to cotton goods;

W-hil'e-'- methyleneanthrone and a number of substituted methyleneanthronecompounds are known compounds, it is' here-noted that methyleneanthrone can he prepared as described by K. H. Meyer, Liebigs Annalen', vol; 420; page 135 (1920). Substituted methylene anthrone compounds can be prepared hy the method just referredi to fan the preparation-0f methyleneanthrone; by-theiuse of. a; substituted" anthrone eompmmdi in place of anthrcnei Wei-claim:

1 The compound's hav'ing the general formulwz wfiereiiifRi-staiids for a'i-thien yl' radical-selected fronn the group? consisting of aim-unsubstituted thienyl nucleus joined to the 7,8-benzo-pyrene- 1,6-dione nucleus through the carbon atoms in its 2- and 3-po'sitionsi-aiiunsubstituted thienyl nucleus joined to thei7,8 benzo-pyrene-L6-dione nucleus through the carbon atoms in its 3- and -positions anda 2',5 -=di'cmorothienyl nucleus joined to the 7,8-benZb-p3r'rene-L6-dione nucleus through the carbon atoms in its 3- and 4-positions and X represents afiniember selected from the group consisting of a chlorine atom, a

bromine atom, a:fluorine atomanda--methy1- ero'un v 2. #The compound having. the formula:

3. The compound having the formula:

4. The compound having the formula:

5. The compound having the formula:

10 6. The compound having the formula:

'7. The process of preparing 2,3-thienyl-'7,8- benzo-pyrene-1,6-dione compounds which comprises heating a B2 l-thenoylbenzanthrone compound with a mild oxidizing agent at a temperature of about C. to about C. in the presence of an AlC13-NaC1 melt.

8. The process of preparing 2,3-(2,3-thienyl) 7,8 benzopyrene-1,6 dione which comprises heating Bz-1-(2-thenoy1) benzanthrone with a mild oxidizing agent at a temperature of about 160 C. to about 180 C. in the presence of an AlCls-NaCl melt.

JAMES M. STRALEY. RAYMOND C. HARRIS.

N 0 references cited. 

1. THE COMPOUNDS HAVING THE GENERAL FORMULA: 